Process of improving motor fuel



Sept. 6, 1938. w. E. KuENTzEL er A1. 2,129,142

I PROCESS 0F IMPROVING MOTOR FUEL Filed kann 25, 193e f\ f\ =a=s l U l-Q LQ :G s s l.:

l 1 l s l l g. f' s e s s v ...n Y g o: a o: .il ";l) f//j O RS'l-/ENTZE L A. GEMS/MN BATCHELDER ATTORNEY Patented Sept. 6, `1938OFFICE Pnocnss or IMPROVING Mo'roa FUEL Ward E. Kuentzel, Whiting, Ind.,Theodore A. Geissman. Minneapolis, Minn., and Howard 1L Batch'eider,Hammond, Ind., assignors to Standard Oil Company, Chicago,

"Indiana Ill., a corporation of Application March 25, 1936, Serial No.70,802

10 Claims.

This inventionrelates to a process for treating internal combustionmotor fuel to improve the anti-knock properties thereof and pertainsmore particularly to a process for improving the antiknock properties ofmotor fuel in the presence of a special catalyst.

One of the principal objects of our invention is to provide a processfor improving the antiknock properties of motor fuel wherein theimprovment may be eiiected with minimum loss in yield and with a minimumformation of byproducts unsuitable for motor fuel.

A further object of our invention is to provide a catalytic process forimproving the anti-knock l5 properties of motor fuel which is moreflexible in operation and which enables a selected treatment of separatefractions of the motor fuel. A further object of our invention is toprovide an improved catalyst for effecting the improvement :0 in theanti-knock properties of .the motor fuel.

It has heretofore been proposed to subject hydrocarbons within thegasoline boiling range or a fraction containing principally hydrocarbonswithin the gasoline boiling range to treatment in 5 the presence of acatalyst to improve the antiknock properties thereof. We have found thatgreater benefits may be obtained if the hydrocarbons are treated in thepresence of a catalyst hereinafter described.

D In accordance with our invention the hydrocarbons to be treated, whichmay comprise straight-run or cracked gasoline, heavy naphtha or afraction consisting principally of gasoline constituents, are firstheated to a temperature range, for example, from 850 to 950 F., andthereafter passed in contact with a catalyst composed of a relativelylarge percentage of an oxide taken from the eighth group of the periodictable admixed with a relatively smaller percentage of an oxide from thethird group such as aluminum and boron oxide, for example, andpreferably including a small percentage of sodium or potassium oxide.

The catalyst above specified is preferably in the form of a gel and maybe -made by precipitating and drying the hydroxides of the metalconstituents. For example, ferric and aluminum hydroxides are firstprecipitated from dilute solutions of iron and aluminum salts,preferably nitrates, with ammonia or potassium hydroxide at atemperature of about 60 C. The hydroxides are then admixed, theproportion ranging from 85 to 97 per cent ferric hydroxide and from 2 to14 per cent aluminum hydroxide, preferably 94 per cent of ferriehydroxide to 5 per cent aluminum hydroxide, andthe mixture then washedland filtered. The residue is then kneaded to remove as much Water aspossible and a small amount, preferably about 1 per cent, of potassiumhydroxide added to the mixture during the kneading operation. Thecatalyst may be then dried first at about 100 C. and finally at about150 C.

'The invention will be better explained with reference to theaccompanying drawing which is a schematic illustration of an apparatussuitable for carrying the invention into effect.

Referring to the drawing, the reference character I0 designates acharging line through which the stock to be treated is passed by meansoi' pump II to a heating zone which may be in the form of a furnace I2.The oil, during its passage through the heating zone, is heatedto atemperature in excess of 850 F. and preferably to a temperature rangefrom 850 F. to 950 F. As before mentioned, the original oil may begasoline, heavy naphtha, or a fraction consisting principally ofgasoline constituents. The oil, after being heated to the desiredtemperature Within the heating furnace I2, is passed through transferline `i3 Ainto the bottom of reaction chamber I 4 in which is positioneda bed of catalytic material I5 of the character hereinbefore described.Vapors formed as a result of the heating of the oil in furnace I2 passupwardly through the bed oi catalytic material and are subjected totreatmentfor improving the antiknock properties thereof. Any unvaporizedresidue resulting from the heating operation or the treating operationis withdrawn from the bottom of the reaction chamber I4 through line 20.The reaction products thereafter passl overhead through line i5 to afractionating tower i5 wherein constituents boiling above those desiredin the final distillate are condensed. Condensate formed in the tower iswithdrawn therefrom through line I'l and may be withdrawn from thesystem through line I8 or returned to the heating furnace I2 throughlines I9, I0 and pump II.

Vapors remaining uncondensed in tower i5 pass overhead through line 2|to condenser 22, wherein the desired distillate condenses, and thence toa receiving tank 23 wherein the distillate separates from fixed gases.Fixed gases may be withdrawn from receiving drum 23 through line 24 andthe distillate withdrawn through line 25 to a stabilizer not shown.

While, for simplicity, we have shown but one reaction chamber I4,containing the catalytic material before described, it will beunderstood that a plurality may be provided. connected in series or inparallel and operated simultaneously or' alternately as desired.Moreover, in lieu of a catalytic chamber the catalytic material may bepositioned within the tubes located in the furnace I2 in which case theproducts from the heating coil may pass directly through lines I3 and 26tothe fractionating -tower I8 without passing through a understood thatthe reaction chamber will be lagged to prevent radiation losses andmaintain the desired reaction temperature within the chamber.

As a guide in carrying out the invention to the best advantage thefollowing example will be helpful, it being understood that theinvention is not limited to the specific example given.

A heavy naphtha fraction having an initial boiling point of 150 F., anend point of 415 F., an average boiling point of 321 F., and 90 per centci! at 374 F. and having an octane rating of 37 as determined by theResearch Method, was passed through a bed of catalytic materialconsisting of 94 per cent iron oxide, 5 per cent aluminum oxide andabout l per cent potassium oxide, while at a temperature of 930 F. Theaverage time of contact of the vapors with the catalytic material was1.8 seconds. The reaction products were thereafter fractionated to forma 394 F. end point product which was found to have an octane number ofas compared to the original 3'1 of the fresh feed. Under the time andtemperature conditions of operation no material improvement in theoctane rating of the product would be expected in the absence of thecatalyst.

Having described the preferred embodiment ofthe invention it will beunderstood that it embraces such other modifications and variation as-oome within the spirit and scope thereof and that it is not ourintention to limit the invention except as necessary to distinguish fromprior art.

We claim:

V1. A method of improving the anti-knock properties of internalcombustion motor fuel which comprises passing a hydrocarbon motor fuelthrough and in contact with a bed of catalytic material formed byadmixing 94 parts of ferric hydroxide, 5 parts of aluminum hydroxide andl part of potassium oxide and drying at a temperature of about 150 C.,maintaining said fuel during its passage through said bed at atemperature above 850 F., cooling the treated products and separatingtherefrom a liquid motor fuel having higher anti-knock properties. thanthe initial feed stock.

2. A method of improving the anti-knock properties of internalcombustion motor fuel which comprises passing a hydrocarbon motor fuelproduct through and in contact with a bed of catalytic material formedby admixing 94 parts of ferric hydroxide, 5 1 part of potassium oxideand drying at a temperature of about C., maintaining said fuel duringits passage through said bed at a temperature ranging from about 900 F.to about 950 F.,

vcooling the treated products and separating therefrom a liquid motorfuel having higher anti-knock properties than the initial feed stock.

3. A method of improving the anti-knock properties of internalcombustion motor fuel which comprises passing a hydrocarbon motor fuelproduct through and in contact with a bed of catalytic material formedby admixing 94 parts of ferrichydroxide, 5 parts of aluminum hydroxideand 1 part of potassium oxide and drying at tem chamber Il. It will alsobe f parts of aluminum hydroxide and f a temperature of about iw C.,maintaining said fueldmingitspassagethroughsaidbedata of about 930 1"..cooling the treated products and separating therefrom a liquid motorfuel having higher anti-knock properties than the initial feed stock.

4. A method of improving the anti-knock properties of a hydrocarbonfraction consisting principally of gasoline constituents which comprisescontacting the hydrocarbon fraction with a catalytic'material formed byadmixing 85 to 97% of ferrie hydroxide, hydroxide and about 1% ofpotassium hydroxide and drying the admixture .at a temperature of about150 C., maintaining said hydrocarbon fraction in contact with saidcatalyst for a few seconds while at a temperature within the range ofabout S50-950 F., cooling the treated products and separating therefroma liquid motor fuel having higher anti-knock properties than the chargedfraction of hydrocarbons. v

5. A method of improving the anti-knock properties of a hydrocarbonfraction consisting principally of gasoline constituents which comprisespassing the hydrocarbon fraction through and in contact with a bed ofcatalytic material containing about 94 parts of iron oxide, about 5parts of aluminium oxideand about l part of an alkali metal oxide,maintaining said hydrocarbon fraction in contact with said catalyst fora few seconds while at a temperature within the range of about S50-950F., cooling the treated products and separating therefrom a liquid motorfuel product having higher anti-knock properties than the chargedfraction of hydrocarbons. Y

6. A method of improving the anti-knock prop- 14 to 2% of aluminium'erties of a hydrocarbon fraction consisting principally of gasolineconstituents which comprises contacting the hydrocarbon fraction with acatalytic gel containing about 94 parts of iron oxide, about 5 parts ofaluminium oxide and about l part of potassium oxide, maintaining saidhydrocarbon fraction in contact with said catalyst for a short intervalof time while at a temperature within the range of about 850-950 F.,cooling the treated products and separating therefrom a liquid motorfuel having higher anti-knock properties than the charged fraction ofhydrocarbons.

'7. A method of improving the anti-knock properties of a hydrocarbonfraction consisting principally of gasoline constituents whichcomprisescontacting the hydrocarbon fraction with a catalyticmaterial consistingof an oxide of a metal selected from the group consisting of iron,nickel and cobalt, admixed with a small amount of an oxide selected fromthe group consisting of aluminium oxide and boron oxide, and furtheradmixed with a very small amount of an oxide selected from the groupconsisting of sodium oxide and potassium oxide, maintaining saidhydrocarbon fraction in contact with said catalyst for a short period oftime while at a temperature within the range of about S50-950 F.,cooling the treated products and separating therefrom a liquid motorfuel having higher anti-knock properties than the charged fraction ofhydrocarbons.

8. A method of improving the anti-knock properties of a hydrocarbonfraction consisting principally of gasoline constituents which comprisespassing the hydrocarbon fraction through and in contact with a bed ofcatalytic material containing about 94 parts of iron oxide, about 5parts of aluminum oxide and about l part of an alkali metal oxide,maintaining said hydrocarbon fraction in contact with said catalyst fora few seconds while at a temperature within the range of about 850-950"F., passing the treated hydrocar-y bon fraction into a fractionatingzone, withdrawing uncondensed vapors from the top part of saidfractionating zone, withdrawing condensed products from the bottom partof said fractionating zone and recycling a part ofvthem for furthercontact with the catalytic material.

a. 'I'he method of improving the anti-knock properties of a hydrocarbonfraction consisting principally of gasoline constituents which comprisescontacting the hydrocarbon fraction with a catalytic material formed bymixingr 85 to 97% 2% of aluminum hyoi ferrie hydroxide, 14 to droxideand about 1% of potassium hydroxide and drying the admixture at atemperature of about 150 C.,-rnai1ntaining said hydrocarbon fraction incontact with said catalyst for a short interval oi" time While at atemperature within the range of 3504150 F., cooling the treated productsand separating therefrom a liquid motor fuel having higher anti-knockproperties than the charged fraction of hydrocarbons.

10. A methtod of improving the anti-knock properties of a hydrocarbonfraction consisting principally of gasoline constituents which comprisescontacting the hydrocarbon fraction with a catalytic material formed bymixing 85 to 97% of an hydroxide selected from the group consisting offerrie hydroxide, cobalt hydroxide, 14 to 2% of aluminum hydroxide, andabout 1% of an hydroxide selected from the group consisting of sodiumhydroxide and potassium hydroxide and drying the admixture at anelevated temperature sufiicient to convert substantially all of thehydroxides into oxides, maintaining said hydrocarbon fraction in contactwith said catalyst for a short interval of time While at a temperaturewithin the range of 850-950 F., cooling the treated products andseparating therefrom a liquid motor fuel having higher anti-knockproperties than the charged fraction oi hydrocarloons.

WARD E. KUENTZEL. THEODORE A. GEISSMAN. HOWARD R. BATCHELDER.

nickel hydroxide and

